JPWO2020066496A1 - Manufacturing method of electronic device laminate and electronic device laminate - Google Patents

Abstract

When sealing an electronic device such as an organic EL device with a gas barrier film, it is possible to reduce the thickness of the adhesive layer to prevent deterioration of the element and to produce a highly flexible electronic device laminate. Provided is a method for manufacturing an electronic device laminate capable of being capable of, and an electronic device laminate. A step of preparing a gas barrier film having a heat-sealing layer, an inorganic layer, and an organic layer in this order, and a substrate having a substrate detachably laminated from the sealing layer on the organic layer side of the sealing layer. , A heat crimping step of heating and pressurizing a gas barrier film on an element forming surface having irregularities of an electronic device with the heat fusion layer side toward the element forming surface side, and peeling the substrate from the sealing layer. It has a peeling step, the thickness of the inorganic layer is 100 nm or less, and the glass transition temperature of the heat-sealed layer is 20 ° C to 180 ° C.

Description

The present invention relates to a method for manufacturing an electronic device laminate and an electronic device laminate.

Organic EL (electroluminescence) materials are very sensitive to moisture. Therefore, in an organic EL device using an organic EL material, it is generally known that the organic EL element is sealed with a passivation film having a gas barrier property. Further, as the material for forming the passivation film, inorganic materials such as silicon nitride, silicon oxide and silicon oxide nitride that exhibit gas barrier properties are exemplified.

However, since the organic EL material is sensitive to heat, the passivation film must be formed with low energy so as not to damage the organic EL material when forming the passivation film. Therefore, in order to obtain sufficient gas barrier properties with the passivation film, it is necessary to use a thick passivation film or to form a plurality of layers of passivation film. However, if the passivation film is made thicker or a plurality of layers of passivation film are formed, the flexibility becomes inferior.

On the other hand, a sealing method using an adhesive having high gas barrier performance has been proposed. The method using an adhesive having high gas barrier performance is more flexible than the encapsulation with a passivation film.

However, in a configuration in which the adhesive layer itself has a gas barrier property, the gas barrier property is lower than in a configuration having an inorganic layer as the gas barrier layer. Can not be sufficiently protected and the organic EL element deteriorates.
In addition, the organic EL element may be deteriorated due to the influence of water contained in the adhesive, residual solvent, and the like.

Further, as a configuration of a highly flexible organic EL device, it has been proposed to use a sealing method in which a gas barrier film is bonded via an adhesive (adhesive). In the method using a gas barrier film, an inorganic layer such as silicon nitride, silicon oxide, or silicon nitride silicon oxide that exhibits gas barrier properties is formed on a substrate different from the organic EL element, so that the inorganic layer can be formed with high energy. Therefore, it is possible to form an inorganic layer that is thin and has a high gas barrier property. Therefore, the organic EL device manufactured by the method of sealing the organic EL element using the gas barrier film is more flexible than the organic EL device manufactured by the method of sealing the organic EL element by the passivation film. It can be an EL device. Therefore, a flexible organic EL display and an organic EL device formed on a three-dimensional curved surface can be obtained by combining with a configuration using a resin film as an element substrate.
In addition, the method using a gas barrier film is superior in productivity to sealing with a passivation film.

For example, in Patent Document 1, an organic EL laminate formed by bonding a light emitting element using an organic EL material, an organic EL device having a passivation film covering the light emitting element, and a transparent sealing substrate with an adhesive. The body is a top-emission type in which the organic EL device emits light toward the sealing substrate side, and the sealing substrate has an inorganic film on the support and an organic film as a base of the inorganic film. It is a gas barrier film having one or more combinations of the above, and the surface layer is an inorganic film. , The entire area between the passivation film and the surface inorganic film is filled, and the gap between the passivation film and the surface inorganic film at the end of the organic EL device is the passivation at the position of the light emitting element. An organic EL laminate that is narrower than the gap between the membrane and the surface inorganic membrane is described.

Further, Patent Document 2 describes between a substrate, a gas barrier layer provided on one surface of the substrate and having one or more combinations of an inorganic layer and an organic layer serving as a forming surface of the inorganic layer, and between the substrate and the gas barrier layer. Described is a gas barrier film provided in the above, which has a peeling organic layer which is in close contact with the organic layer and for peeling from the substrate. Patent Document 2 describes that a gas barrier layer is transferred from this gas barrier film onto an organic EL element via an adhesive layer and sealed.

Japanese Unexamined Patent Publication No. 2014-186850 JP-A-2017-043062

However, in the sealing method in which the gas barrier film is bonded via an adhesive, the infiltration of water from the end face of the adhesive layer becomes a problem.

On the other hand, in Patent Document 1, the thickness of the adhesive layer at the end (the gap between the passivation film and the inorganic film) is the thickness at the position of the light emitting element (organic EL element) (between the passivation film and the inorganic film). It is described that the infiltration of water from the end face of the adhesive layer is suppressed by making it narrower than the gap).
However, in the bonding method described in Patent Document 1, even if the thickness of the adhesive layer is thin, it can be made only about 1 μm. It is necessary to provide a highly resistant passivation film. Therefore, although the thickness of the passivation film can be reduced as compared with the configuration having only the passivation film, a certain thickness is required, and it is difficult to obtain higher flexibility.

Further, if the adhesive layer is thick, the organic EL element may be deteriorated due to the influence of water contained in the adhesive, residual solvent, and the like.

Further, even when a transfer type gas barrier film as described in Patent Document 2 is used, there is the same problem as in Patent Document 1.

As described above, in order to suppress the infiltration of water from the end face of the adhesive layer, it is necessary to reduce the thickness of the adhesive layer on the end face. Further, it is necessary to make the thickness of the adhesive layer thinner in order to suppress the influence of moisture and residual solvent contained in the adhesive.
However, in the organic EL device, a large number of organic EL elements are arranged and formed on the element substrate, and the surface of the organic EL device has irregularities. When sealing an organic EL device with a gas barrier film, a large number of organic EL elements are covered and sealed with the gas barrier film. Therefore, it is necessary to control the gap (thickness of the adhesive layer) between the organic EL device and the gas barrier film to be thinner on the uneven surface to bond the gas barrier film. It is difficult to control the thickness of the adhesive layer to be thin. Patent Documents 1 and 2 do not describe a bonding method capable of reducing the thickness of the adhesive layer when the gas barrier film is bonded to such an uneven surface.

An object of the present invention is to solve such a problem, and when an electronic device such as an organic EL device is sealed with a gas barrier film, the thickness of the adhesive layer can be reduced to prevent deterioration of the element. Another object of the present invention is to provide a method for manufacturing an electronic device laminate capable of producing a highly flexible electronic device laminate, and an electronic device laminate.

The present invention solves the problem by the following configuration.
[1] Prepare a gas barrier film having a sealing layer having a heat-sealing layer, an inorganic layer, and an organic layer in this order, and a substrate having a substrate detachably laminated from the sealing layer on the organic layer side of the sealing layer. And the process to do
A heat crimping step of heating and pressurizing a gas barrier film on an element forming surface having irregularities of an electronic device with the heat fusion layer side toward the element forming surface side.
It has a peeling step of peeling the substrate from the sealing layer.
The thickness of the inorganic layer is 100 nm or less,
A method for manufacturing an electronic device laminate in which the glass transition temperature of the heat-sealed layer is 20 ° C to 180 ° C.
[2] The electron according to [1], wherein in the heat crimping step, the heating temperature and the pressurizing pressure are adjusted so that the distance between the inorganic layer and the electronic device at the end after the heat crimping is less than 100 nm. A method for manufacturing a device laminate.
[3] The method for producing an electronic device laminate according to [1] or [2], wherein the electronic device is an organic electroluminescence device.
[4] The method for producing an electronic device laminate according to any one of [1] to [3], wherein the gas barrier film is heated and pressurized with a roller in the heat crimping step.
[5] The method for manufacturing an electronic device laminate according to any one of [1] to [4], wherein heating is performed from the substrate side in the heat crimping step.
[6] The method for manufacturing an electronic device laminate according to [5], wherein heating is performed from the electronic device side in the heat crimping step.
[7] The method for manufacturing an electronic device laminate according to [6], wherein the heating temperature on the substrate side is higher than the heating temperature on the electronic device side.
[8] The method for producing an electronic device laminate according to any one of [1] to [7], wherein the substrate is a triacetyl cellulose film.
[9] The method for manufacturing an electronic device laminate according to any one of [1] to [8], wherein the thickness of the substrate is 0.1 μm to 100 μm.
[10] An electronic device having an uneven element forming surface and
It has a heat-sealing layer, an inorganic layer, and a transfer layer having an organic layer in this order, which are laminated on the element forming surface.
The thickness of the inorganic layer is 100 nm or less,
The glass transition temperature of the heat-sealed layer is 20 ° C to 180 ° C.
An electronic device laminate in which the distance between the inorganic layer and the electronic device at the end is 100 nm or less.
[11] The electronic device laminate according to [10], wherein the electronic device is an organic electroluminescence device.

According to the present invention, when an electronic device such as an organic EL device is sealed with a gas barrier film, the thickness of the adhesive layer can be reduced to prevent deterioration of the element, and a highly flexible electronic device laminate can be prevented. It is possible to provide a method for producing an electronic device laminate capable of producing the above, and an electronic device laminate.

It is sectional drawing which shows typically an example of the transfer type gas barrier film used in the manufacturing method of the electronic device laminated body of this invention. It is a figure for demonstrating an example of the manufacturing method of the electronic device laminated body of this invention. It is a figure for demonstrating an example of the manufacturing method of the electronic device laminated body of this invention. It is a figure for demonstrating an example of the manufacturing method of the electronic device laminated body of this invention. It is sectional drawing which shows typically an example of the electronic device laminated body of this invention produced by the manufacturing method of the electronic device laminated body of this invention.

Hereinafter, a method for manufacturing the electronic device laminate of the present invention and an embodiment of the electronic device laminate will be described with reference to the drawings.

[Manufacturing method of electronic device laminate]
The method for producing an electronic device laminate of the present invention is:
A step of preparing a gas barrier film having a heat-sealing layer, an inorganic layer, and an organic layer in this order, and a substrate having a substrate detachably laminated from the sealing layer on the organic layer side of the sealing layer. ,
A heat crimping step of heating and pressurizing a gas barrier film on an element forming surface having irregularities of an electronic device with the heat fusion layer side toward the element forming surface side.
It has a peeling step of peeling the substrate from the sealing layer.
The thickness of the inorganic layer is 100 nm or less,
This is a method for manufacturing an electronic device laminate in which the glass transition temperature of the heat-sealed layer is 20 ° C. to 180 ° C.

Hereinafter, an example of the method for manufacturing the electronic device laminate of the present invention will be described with reference to FIGS. 1 to 5.

The method for producing an electronic device laminate of the present invention (hereinafter, also referred to as the production method of the present invention) includes a sealing layer having a heat-sealing layer, an inorganic layer, and an organic layer in this order, and an organic layer of the sealing layer. A step of preparing a gas barrier film having a substrate detachably laminated from the sealing layer on the side (FIG. 1), and a heat-sealing layer side of the gas barrier film on an element forming surface having irregularities of an electronic device. It has a heat crimping step (FIGS. 2 to 4) of heating and pressurizing and crimping toward the element forming surface side, and a peeling step (FIGS. 4 and 5) of peeling the substrate from the sealing layer.

<Gas barrier film>
FIG. 1 shows a cross-sectional view schematically showing a gas barrier film used in the method for producing an electronic device laminate of the present invention.
The gas barrier film 40 shown in FIG. 1 has a heat-sealing layer 30, an inorganic layer 16, an organic layer 14, and a substrate 32 in this order. The heat-sealing layer 30, the inorganic layer 16, and the organic layer 14 are sealing layers 12 that can be peeled off from the substrate 32. That is, the gas barrier film 40 is formed so as to be peelable at the interface between the substrate 32 and the organic layer 14. The gas barrier film 40 is a transfer type gas barrier film capable of transferring the sealing layer 12 to an electronic device.

In the gas barrier film 40, the inorganic layer 16 is a layer that mainly exhibits gas barrier properties, and the organic layer 14 is a layer that serves as a base layer for the inorganic layer 16. Further, the heat-sealing layer 30 is a layer that flows by heating when the gas barrier film 40 is attached to an electronic device and exhibits adhesiveness.

Here, in the present invention, the thickness of the inorganic layer 16 is 100 nm or less.
The glass transition temperature Tg of the heat-sealing layer 30 is 20 ° C. to 180 ° C.
Each layer of the gas barrier film 40 will be described in detail later.

<Heat crimping process>
The thermal crimping step is a step of crimping the gas barrier film 40 as described above onto the element forming surface of the electronic device 50.
In the thermal crimping step, first, as shown in FIG. 2, an electronic device (organic EL device) 50 in which a plurality of organic EL (electroluminescence) elements 54 are formed on the element substrate 52 is placed on a table 100. .. Further, the heat-sealing layer 30 of the gas barrier film 40 is made to face the surface of the electronic device 50 on the organic EL element 54 side (hereinafter, also referred to as an element forming surface).

Next, as shown in FIG. 3, the gas barrier film 40 is pressure-bonded to the electronic device 50 using the roller 102. At that time, the roller 102 has a heating means, and the gas barrier film 40 is pressurized while being heated by the roller 102.
Further, as a preferred embodiment, the table on which the electronic device 50 is placed also has a heating means, and the electronic device 50 side is also heated.

When the gas barrier film 40 is heated during pressurization, the heat-sealing layer 30 flows and exhibits adhesiveness. As a result, the gas barrier film 40 is attached to the element forming surface of the electronic device 50 (FIG. 4).

Here, when a conventional adhesive layer is used as a material for adhering the gas barrier film and the electronic device, the thickness of the adhesive layer cannot be significantly changed even if pressure or heating is applied at the time of bonding. Therefore, it is difficult to make the thickness of the adhesive layer thinner.
On the other hand, as a method of making the thickness of the adhesive layer thinner, a method of applying a liquid adhesive to the element forming surface of the electronic device and then adhering the gas barrier film is also conceivable, but the inorganic layer of the gas barrier film is exposed. If the bonding is performed in this state, the inorganic layer may be cracked and the gas barrier property may be deteriorated. When a protective layer made of resin is provided to prevent the inorganic layer from cracking, the inorganic layer can be prevented from cracking, but the protective layer becomes thicker, which makes it difficult to follow the unevenness of the element forming surface of the electronic device. In addition, the organic EL element may be deteriorated due to the influence of water contained in the protective layer, residual solvent, and the like.

On the other hand, in the production method of the present invention, a heat-sealing layer 30 having a glass transition temperature of 20 ° C. to 180 ° C. and being melted by heating is used as a material for adhering the gas barrier film 40 and the electronic device 50. As a result, when the gas barrier film 40 is attached to the element forming surface of the electronic device 50, the heat fusion layer flows and flows into the recesses of the element forming surface, so that the thickness of the heat fusion layer 30 becomes very large. The organic EL element 54 of the electronic device 50 and the gas barrier film 40 can be made thinner, or the heat-sealing layers 30 can be made to be scattered between the inorganic layer 16 and the electronic device 50. The distance between the inorganic layer 16 and the distance between the electronic device 50 (device substrate 52) and the inorganic layer 16 of the gas barrier film 40 at the end can be reduced.
As described above, the manufacturing method of the present invention can make the distance between the inorganic layer 16 and the electronic device 50 (thickness of the heat-sealing layer 30) on the end face after heat-bonding very small, and thus the present invention. The electronic device laminate 10 produced by the above manufacturing method can prevent the infiltration of moisture from the end face of the heat-sealing layer 30 and prevent the deterioration of the organic EL element 54.

Further, since the heat-sealing layer 30 is solid until it is heated, the inorganic layer 16 of the gas barrier film 40 can be protected, and the inorganic layer 16 can be prevented from cracking during transportation, bonding, and the like. Can be done.
Further, since the heat-sealing layer 30 is a heat-sealing solid, it can be free of (less) residual solvent and water. Therefore, deterioration of the organic EL element 54 due to the residual solvent and moisture can be prevented.

Further, when the gas barrier film 40 is bonded to the element forming surface of the electronic device 50, the heat fusion layer flows and flows into the recess of the element forming surface, so that between the gas barrier film 40 and the electronic device 50 at the time of bonding. The gas (air) present in the can be efficiently removed. Therefore, it is possible to prevent gas (air) from remaining in the recesses and the like on the element forming surface of the manufactured electronic device laminate 10.

Further, in the present invention, since the thickness of the inorganic layer 16 of the gas barrier film 40 is 100 nm or less and has flexibility, the gas barrier film 40 is pressure-bonded to the uneven element forming surface of the electronic device 50 in the heat-bonding step. However, as shown in FIG. 4, since the inorganic layer 16 can be curved according to the unevenness of the element forming surface without cracking, it is curved so that the distance between the inorganic layer 16 and the electronic device 50 becomes small at the end portion. can do.

Further, in the present invention, as the gas barrier film 40, a transfer type gas barrier film 40 in which the sealing layer 12 and the substrate 32 can be peeled off is used. Therefore, when the gas barrier film 40 is crimped to the element forming surface of the electronic device 50 in the thermal crimping step, the substrate 32 can be partially peeled off from the sealing layer 12, and the sealing layer 12 including the inorganic layer 16 is the element. It becomes easier to follow the unevenness of the formed surface. As a result, the distance between the inorganic layer 16 after crimping and the electronic device 50 can be made smaller.

Further, since the heat-sealing layer 30 exhibits fluidity only in the heated portion and adhesiveness is obtained, it can be bonded to an arbitrary portion. Therefore, for example, when the electronic device 50 has a three-dimensional shape and it is difficult to completely bond the sealing layer 12, only the end portion is bonded, and the sealing layer 12 covers the element forming surface of the electronic device 50. In this way, it can be sealed, or it can be additionally transferred and sealed to a portion where the barrier property needs to be particularly enhanced due to the shape, physical properties, and the like of the element.

Here, in the heat crimping step, the heating temperature and the pressurizing pressure are adjusted so that the distance between the inorganic layer 16 and the electronic device 50 (element forming surface) at the end portion after the heat crimping is 100 nm or less. It is preferable to do so.
By setting the distance between the inorganic layer 16 and the electronic device 50 (element forming surface) at the end after heat crimping to 100 nm or less, the infiltration of moisture from the end of the heat-sealing layer 30 is suitably prevented. can do.
The heating temperature and the pressure to be pressurized depend on the material and thickness of the heat-sealing layer 30, the thickness and hardness of the substrate 32, the uneven state of the electronic device 50, the required thickness of the heat-sealing layer, and the like. It may be set appropriately.

In the heat bonding step, the heating temperature of the gas barrier film 40 is preferably Tg or higher, more preferably Tg + 50 ° C to Tg + 5 ° C, and more preferably Tg + 30 ° C to Tg + 20 ° C. Is even more preferable. By setting the heating temperature of the gas barrier film 40 within the above range, the heat-sealing layer 30 can be reliably flowed during crimping.

Further, as described above, the electronic device 50 may be heated in the heat crimping step. Here, if the heating temperature on the electronic device 50 side is too high, the organic EL element 54 may be damaged. Further, when a resin film is used as the element substrate 52, the element substrate 52 may be deformed due to heat shrinkage or the like, and may not be uniformly bonded to the gas barrier film 40. Therefore, when heating from the electronic device 50 side, it is preferable that the heating temperature on the electronic device 50 side is lower than the heating temperature on the gas barrier film 40 side. Specifically, it is preferably Tg + 10 ° C to Tg + 5 ° C, and more preferably Tg + 5 ° C to Tg ° C.

Further, in the heat bonding step, the pressure applied to the gas barrier film 40 and the electronic device 50 is preferably 0.001 MPa to 5 MPa, more preferably 0.01 MPa to 1 MPa, and even more preferably 0.1 MPa to 0.5 MPa.
By setting the pressure applied to the gas barrier film 40 and the electronic device 50 to 0.01 MPa or more, the heat-sealing layer 30 flowing by heating is moved, and the inorganic layer 16 of the gas barrier film 40 and the element of the electronic device 50 are moved. The thickness of the heat-sealing layer 30 can be reduced by shortening the distance from the forming surface. On the other hand, if the pressure is too high, the inorganic layer 16 may be cracked or the organic EL element 54 may be damaged. Therefore, the pressure is preferably 5 MPa or less.

Further, in the example shown in FIG. 3, a roller is used as a device for crimping the gas barrier film 40 to the electronic device 50 in the heat crimping step, but the present invention is not limited to this, and a pressurizing device using a piston and a balloon type addition device are used. A known pressurizing device such as a pressure device can be used.

Further, when the pressurization is performed by a roller, the roller surface is preferably made of a flexible rubber material. By using a roller whose surface is made of a rubber material, it is possible to prevent the inorganic layer 16 of the gas barrier film 40 from being damaged by the unevenness of the element forming surface of the electronic device 50, and the gas barrier film 40 and the electronic device 50 are uniformly bonded together. be able to.

Further, the member that supports the back surface side of the electronic device 50 may be a smooth and highly rigid member, and as shown in FIG. 2, a plate-shaped table having a flat mounting surface may be used. Alternatively, it may be a roller. When a table is used, the gas barrier film 40 and the electronic device 50 may not be uniformly bonded due to the air remaining between the electronic device 50 and the table. In this respect, it is preferable to use a roller.

Further, the heating means included in the roller and / or the table is not particularly limited, and a known heating means may be used.

Further, in the example shown in FIG. 3, the structure is such that heating and pressurization are performed simultaneously by a roller, but the present invention is not limited to this, and the gas barrier film may be pressure-bonded after being heated.

Further, it is preferable that the heat crimping step is performed by reducing the pressure to atmospheric pressure or lower. By performing the heat bonding step under reduced pressure, it is possible to prevent air from remaining between the gas barrier film 40 and the electronic device 50 when the gas barrier film 40 and the electronic device 50 are bonded together.

<Peeling process>
In the peeling step, as shown in FIG. 5, the substrate 32 of the gas barrier film 40 is peeled from the sealing layer 12 after the heat bonding step. The overall thickness of the electronic device laminate 10 produced by peeling the substrate 32 can be reduced to increase the flexibility.

According to the manufacturing method of the present invention, the electronic device laminate 10 as shown in FIG. 5 can be manufactured by carrying out each of the above steps.

[Electronic device laminate]
The electronic device laminate of the present invention produced by the production method of the present invention is
Electronic devices with uneven element forming surfaces and
It has a heat-sealing layer, an inorganic layer, and a transfer layer having an organic layer in this order, which are laminated on the element forming surface.
The thickness of the inorganic layer is 100 nm or less,
The glass transition temperature of the heat-sealed layer is 20 ° C to 180 ° C.
It is an electronic device laminate in which the distance between the inorganic layer and the electronic device at the end is 100 nm or less.

The electronic device laminate 10 shown in FIG. 5 has an electronic device (organic EL device) 50 having an element substrate 52 and an organic EL element 54, and a sealing layer 12 having a heat fusion layer 30, an inorganic layer 16 and an organic layer 14. And have.
In the sealing layer 12, the heat-sealing layer 30 is in contact with the surface (element forming surface) on which the organic EL element 54 of the electronic device 50 is formed, and is laminated on the electronic device 50.

Here, in the electronic device laminate 10, the thickness of the inorganic layer 16 is 100 nm or less. By setting the thickness of the inorganic layer 16 to 100 nm or less, the flexibility of the inorganic layer 16 can be increased so that the inorganic layer 16 can be curved following the unevenness of the element forming surface of the electronic device 50. Therefore, the distance between the inorganic layer 16 and the electronic device 50 at the end portion can be reduced, and the infiltration of water from the end portion of the heat fusion layer 30 can be prevented.

Further, in the electronic device laminate 10, the glass transition temperature of the heat-sealing layer 30 is 20 ° C to 180 ° C. Since the heat-sealed layer 30 having a glass transition temperature in the above range is melted by heating, the heat-sealed layer 30 is heated and flowed as in the above-mentioned manufacturing method to be between the inorganic layer 16 and the electronic device 50. The distance can be small.

Further, in the electronic device laminate 10, the distance between the inorganic layer 16 and the electronic device 50 at the end, that is, the thickness of the heat fusion layer 30 is set to 100 nm or less, so that the heat fusion layer 30 can be viewed from the end face. It is possible to suppress the infiltration of water.
The distance between the inorganic layer 16 and the electronic device 50 at the end is determined by cutting the electronic device laminate 10 in the thickness direction and observing the cross section with a microscope, SEM (scanning electron microscope), microscope, or the like. Can be measured.

Hereinafter, the parts constituting the electronic device laminate and the substrate will be described in detail.

<Board>
As the substrate 32, a known sheet-like material (film, plate-like material) used as a substrate (support) in various gas barrier films and various laminated functional films can be used.
Further, as the substrate 32, various sheet-like materials used as separators (light peeling separator and heavy peeling separator) in various optical transparent adhesives (OCA (Optical Clear Adhesive)) can also be used.

The material of the substrate 32 is not limited, and the organic layer 14, the inorganic layer 16, and the heat-sealing layer 30 can be formed, and further, the material is not dissolved by the solvent contained in the composition for forming the organic layer 14. As long as it is, various materials can be used. As the material of the substrate 32, various resin materials are preferably exemplified.
Examples of the material of the substrate 32 include polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), and polyacrytonitrile (PAN). ), Polyimide (PI), transparent polyimide, polymethyl methacrylate resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS) ), Cycloolefin copolymer (COC), cycloolefin polymer (COP), triacetylcellulose (TAC), ethylene-vinyl alcohol copolymer (EVOH) and the like.
Among them, triacetyl cellulose (TAC) is preferably used as the material of the substrate 32 because it can be easily formed so as to be peelable at the interface with the organic layer 14.

The thickness of the substrate 32 can be appropriately set according to the application, the material, and the like.
Although the thickness of the substrate 32 is not limited, the transfer type gas barrier film can obtain a transfer type gas barrier film having good flexibility, which can sufficiently secure the mechanical strength of the transfer type gas barrier film. It is possible to reduce the weight and thickness, obtain a transfer type gas barrier film that can be easily peeled off from the sealing layer 12 during transfer, and easily follow the unevenness of the element forming surface of the electronic device 50 in the heat bonding process. Therefore, 120 μm to 5 μm is preferable, and 100 μm to 15 μm is more preferable.

<Organic layer>
The organic layer 14 is a layer constituting the sealing layer 12, and is a layer serving as a base layer for appropriately forming the inorganic layer 16. Further, the organic layer 14 is an organic layer to which the substrate 32 is detachably attached. That is, the organic layer 14 is an organic layer that can be peeled off from the substrate 32. Therefore, the adhesion between the organic layer 14 and the inorganic layer 16 is stronger than the adhesion between the substrate 32 and the organic layer 14.
As will be described later, the inorganic layer 16 formed on the surface of the organic layer 14 is preferably formed by plasma CVD (Chemical Vapor Deposition). Therefore, when the inorganic layer 16 is formed, the organic layer 14 is etched by plasma, and the organic layer 14 and the inorganic layer 16 have a component of the organic layer 14 and a component of the inorganic layer 16 and are mixed. A layer like a layer is formed. As a result, the organic layer 14 and the inorganic layer 16 are brought into close contact with each other with a very strong adhesive force.
Therefore, the adhesion between the organic layer 14 and the inorganic layer 16 is much stronger than the adhesion between the substrate 32 and the organic layer 14, and even if the substrate 32 is peeled from the organic layer 14, the organic layer 14 and the inorganic layer 14 are adhered to each other. 16 does not peel off.
The thickness of the organic layer 14 is the thickness of a layer composed of only the components forming the organic layer 14, which does not include the above-mentioned mixed layer.

Further, since the organic layer 14 is a base layer for properly forming the inorganic layer 16, the organic layer 14 formed on the surface of the substrate 32 has irregularities on the surface of the substrate 32 and foreign substances adhering to the surface. Embed. As a result, the formation surface of the inorganic layer 16 is made appropriate, and the inorganic layer 16 can be formed appropriately.
By forming the inorganic layer 16 on the organic layer 14 that makes the substrate 32 peelable, a transfer type gas barrier film that allows the substrate 32 to be peeled off is realized.
Further, the organic layer 14 acts as a protective layer for protecting the inorganic layer 16 after the substrate 32 is peeled off.

Since the organic layer 14 is exposed to a high temperature when the inorganic layer 16 is formed, it is preferable that the organic layer 14 has high heat resistance. Specifically, the organic layer 14 preferably has a glass transition point (Tg) of 175 ° C. or higher, more preferably 200 ° C. or higher, and even more preferably 250 ° C. or higher.
As described above, the inorganic layer 16 formed on the surface of the organic layer 14 is preferably formed by plasma CVD. By setting the Tg of the organic layer 14 to 180 ° C. or higher, etching and volatilization of the organic layer 14 by plasma when forming the inorganic layer 16 is suitably suppressed, and the appropriate organic layer 14 and the inorganic layer 16 are suitable. It is preferable in that it can be formed in.
The upper limit of Tg of the organic layer 14 is not limited, but is preferably 500 ° C. or lower.

Further, for the same reason as Tg, the resin forming the organic layer 14 preferably has a large molecular weight to some extent.
Specifically, the resin forming the organic layer 14 preferably has a molecular weight (weight average molecular weight (Mw)) of 500 or more, more preferably 1000 or more, and further preferably 1500 or more.

The Tg of the organic layer 14 may be specified by a known method using a differential scanning calorimeter (DSC) or the like. The molecular weight may also be measured by a known method using gel permeation chromatography (GPC) or the like. When a commercially available product is used, the catalog values may be used for the Tg and the molecular weight of the organic layer 14.
The same applies to the heat-sealing layer 30 described later with respect to the above points.

As a material for forming the organic layer 14, various organic layers (organic layers) used as a base layer of an inorganic layer in a known gas barrier film can be used. The organic layer 14 is, for example, a layer made of an organic compound obtained by polymerizing (crosslinking, curing) a monomer, a dimer, an oligomer, or the like. The composition for forming the organic layer 14 may contain only one type of organic compound, or may contain two or more types of organic compounds.
The organic layer 14 contains, for example, a thermoplastic resin, an organosilicon compound, and the like. Thermoplastic resins include, for example, polyester, (meth) acrylic resin, methacrylate-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane. , Polyether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic modified polycarbonate, fluorene ring-modified polyester, acrylic compound and the like. Examples of the organosilicon compound include polysiloxane.

The organic layer 14 preferably contains a polymer of a radical curable compound and / or a cationic curable compound having an ether group from the viewpoint of excellent strength and a glass transition point.
From the viewpoint of lowering the refractive index of the organic layer 14, the organic layer 14 preferably contains a (meth) acrylic resin containing a polymer such as a (meth) acrylate monomer or an oligomer as a main component. By lowering the refractive index of the organic layer 14, the transparency is increased and the light transmittance is improved.

The organic layer 14 is more preferably bifunctional or more, such as dipropylene glycol di (meth) acrylate (DPGDA), trimerol propanetri (meth) acrylate (TMPTA), and dipentaerythritol hexa (meth) acrylate (DPHA). Contains a (meth) acrylic resin containing a polymer such as a (meth) acrylate monomer, dimer and oligomer as a main component, and more preferably a polymer such as a trifunctional or higher functional (meth) acrylate monomer, dimer and oligomer. Contains (meth) acrylic resin whose main component is. Moreover, you may use a plurality of these (meth) acrylic resins. The main component refers to the component having the largest content mass ratio among the contained components.

Further, the organic layer 14 can be made peelable by forming the organic layer 14 with a resin having an aromatic ring.
The organic layer 14 preferably contains a resin containing a bisphenol structure as a main component. The organic layer 14 more preferably contains polyarylate (polyarylate resin (PAR)) as a main component. As is well known, polyarylate is an aromatic polyester composed of a polycondensate of a dihydric phenol such as bisphenol represented by bisphenol A and a dibasic acid such as phthalic acid (terephthalic acid, isophthalic acid). ..
By using the organic layer 14 as the main component of a resin containing a bisphenol structure, and particularly by using the organic layer 14 as the main component of polyarylate, the adhesion between the substrate 32 and the organic layer 14 is appropriate and easy. The substrate 32 can be peeled off. Further, since it has appropriate flexibility, damage (cracking, cracks, etc.) of the inorganic layer 16 when peeling the substrate 32 can be prevented, and since it has high heat resistance, an appropriate inorganic layer 16 can be stably formed, after transfer. It is preferable in that it is possible to prevent deterioration of the performance of the organic thin film transistor and to increase the flexibility as an organic thin film transistor.
The main component refers to the component having the largest content mass ratio among the contained components.

When the organic layer 14 is formed of various resins having an aromatic ring, the organic layer 14 may be formed by using a commercially available product as long as it is a resin having an aromatic ring.
Commercially available resins that can be used to form the organic layer 14 include Unifiner (registered trademark) and U-polymer (registered trademark) manufactured by Unitika Ltd., and Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Inc. Trademark) and the like are exemplified.

The thickness of the organic layer 14 is not limited, but is preferably 0.2 to 6 μm, more preferably 0.5 to 5 μm, and even more preferably 1 to 3 μm.
By setting the thickness of the organic layer 14 to 0.2 μm or more, an appropriate inorganic layer 16 can be stably formed, mechanical strength that is not torn at the time of peeling can be maintained, and good peeling can be performed. It is preferable in that it does not receive. Further, by setting the thickness of the organic layer 14 to 6 μm or less, the gas barrier film 40 can be made lighter and thinner, a highly transparent gas barrier film can be obtained, and good peelability of the substrate 32 can be obtained. It is preferable in that it can be cured uniformly at the time of curing, the content of residual solvent can be suppressed, and high flexibility can be obtained.
The thickness of the organic layer 14 is the thickness of a layer composed of only the components forming the organic layer 14, which does not include the above-mentioned mixed layer.

The organic layer 14 can be formed by a known method depending on the material.
For example, the organic layer 14 is a coating method in which a composition (resin composition) in which a resin (organic compound) or the like to be the organic layer 14 is dissolved in a solvent is prepared, applied to a substrate 32, and the composition is dried. Can be formed. In the formation of the organic layer 14 by the coating method, if necessary, the dried composition may be further irradiated with ultraviolet rays to polymerize (crosslink) the resin (organic compound) in the product.
The composition for forming the organic layer 14 preferably contains an organic solvent, a surfactant, a silane coupling agent, and the like in addition to the organic compound.

The organic layer 14 is preferably formed by roll-to-roll. In the following description, "roll to roll" is also referred to as "RtoR".
As is well known, RtoR is a sheet in which a sheet-like material is sent out from a roll formed by winding a long sheet-like material, and a film is formed while transporting the long sheet in the longitudinal direction. This is a manufacturing method in which a material is wound into a roll. By using RtoR, high productivity and production efficiency can be obtained.

The organic layer 14 needs to be formed so as to be detachable from the substrate 32. Therefore, as described above, a material having peelability may be used as the material of the organic layer 14, or a peeling layer may be provided between the organic layer 14 and the substrate 32. As the release layer, a conventionally known release layer can be appropriately used.

The peeling force between the substrate 32 and the organic layer 14 is preferably 0.01 to 2N / 25 mm, more preferably 0.05 to 1N / 25 mm, and even more preferably 0.1 to 0.8 N / 25 mm.

<Inorganic layer>
The inorganic layer 16 is a thin film containing an inorganic compound and is formed on at least the surface of the organic layer 14. In the sealing layer 12, the inorganic layer 16 mainly exhibits gas barrier performance.
On the surface of the substrate 32, there are regions such as irregularities and foreign substances where it is difficult for the inorganic compound to form a film. As described above, by providing the organic layer 14 on the surface of the substrate 32 and forming the inorganic layer 16 on the organic layer 14, the region where the inorganic compound is difficult to form is covered. Therefore, the inorganic layer 16 can be formed without a gap on the forming surface of the inorganic layer 16.

The material of the inorganic layer 16 is not limited, and various kinds of known inorganic compounds used for the gas barrier layer, which are composed of inorganic compounds exhibiting gas barrier performance, can be used.
Examples of the material of the inorganic layer 16 include metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metals such as aluminum carbide. Carbides; Silicon oxides such as silicon oxide, silicon oxide, acid carbide, silicon oxide nitride; Silicon nitrides such as silicon nitride and silicon nitride; Silicon carbides such as silicon carbide; These hydrides; These two types Examples thereof include the above mixtures; and inorganic compounds such as these hydrogen-containing substances. Mixtures of two or more of these are also available.
Among them, silicon nitride, silicon oxide, silicon oxynitride, aluminum oxide, and a mixture of two or more of these are preferably used because they have high transparency and can exhibit excellent gas barrier performance. Among them, silicon-containing compounds are preferably used, and among them, silicon nitride is preferably used in that it can exhibit excellent gas barrier performance.

As described above, the thickness of the inorganic layer 16 is 100 nm or less.
From the viewpoint of flexibility and gas barrier property, the thickness of the inorganic layer 16 is preferably 50 nm or less, more preferably 5 to 50 nm, and even more preferably 10 to 30 nm.
By setting the thickness of the inorganic layer 16 to 2 nm or more, it is preferable in that the inorganic layer 16 that stably exhibits sufficient gas barrier performance can be formed. Further, the inorganic layer 16 is generally brittle, and if it is too thick, cracks, cracks, peeling, etc. may occur, but cracks occur when the thickness of the inorganic layer 16 is 50 nm or less. This can be prevented more preferably. In addition, the flexibility can be increased.

The inorganic layer 16 can be formed by a known method depending on the material.
For example, plasma CVD such as CCP (Capacitively Coupled Plasma) -CVD and ICP (Inductively Coupled Plasma) -CVD, sputtering such as atomic layer deposition (ALD), magnetron sputtering and reactive sputtering, and vacuum. Various vapor deposition methods such as vapor deposition are preferably used.
Above all, as described above, plasma CVD such as CCP-CVD and ICP-CVD is preferably used in that the adhesion between the organic layer 14 and the inorganic layer 16 can be improved.
The inorganic layer 16 is also preferably formed by RtoR.

<Heat fusion layer>
The heat-sealing layer 30 is for adhering the gas barrier film 40 to the element forming surface of the electronic device 50.
The heat-sealing layer 30 also acts as a protective layer that protects the inorganic layer 16 that exhibits gas barrier performance.

In the present invention, the heat-sealing layer 30 uses a hot melt adhesive (HMA (Hot Melting Adhesive)). Specifically, the heat-sealing layer 30 made of a hot-melt adhesive is a heat-sealing layer that is solid at room temperature and flows when heated to exhibit adhesiveness. In the present invention, the normal temperature is 23 ° C.
By using a hot melt adhesive as the heat-sealing layer 30, the gas barrier performance can be further improved as compared with the conventional transfer type gas barrier film.

The heat-sealing layer 30 preferably flows at 30 to 200 ° C. to exhibit adhesiveness, and the heat-sealing layer 30 more preferably flows at 40 to 180 ° C. to exhibit adhesiveness. It is more preferable to flow at ~ 150 ° C. to develop adhesiveness.
When the heat-sealing layer 30 flows at room temperature to exhibit adhesiveness, foiling is likely to occur during cutting and transfer of the gas barrier film, resulting in deterioration of gas barrier performance and the like.
Further, if the temperature at which the fluid flows and develops adhesiveness is too high, the heating temperature required for sticking to the sticking target becomes high, causing thermal damage to the substrate 32, the organic layer 14, and the sticking target. It ends up.

The glass transition temperature Tg of the heat-sealing layer 30 is 20 ° C. to 180 ° C., preferably 25 ° C. to 150 ° C., more preferably 40 ° C. to 140 ° C., and 60 ° C. to 120 ° C. Is even more preferable.
By setting the Tg of the heat-sealing layer 30 in the above range, heat fluidity can be easily obtained, so that adhesiveness and transferability by heating can be improved, adhesion can be performed at a low temperature, and productivity can be improved. preferable.

When a hot melt adhesive is used, the material is not limited as long as the heat-sealing layer 30 is solid at room temperature and can flow by heating to exhibit adhesiveness.
When a hot melt adhesive is used, the heat-sealing layer 30 preferably contains an amorphous resin as a main component, more preferably an acrylic resin as a main component, and polymerizes a single acrylate monomer. It is more preferable to use a resin (acrylic homopolymer (homoacrylic polymer)) as a main component.
By using an amorphous resin, particularly an acrylic resin, as the main component of the heat-sealing layer 30, it is preferable in that a highly transparent gas barrier film can be obtained.
Further, by using an acrylic homopolymer as the main component of the heat-sealing layer 30, in addition to the above-mentioned advantages, it is preferable in that transferability by heat can be improved and blocking is difficult to occur during winding after curing. Further, by forming the heat-sealing layer 30 with an acrylic homopolymer, in addition to the above-mentioned advantages, the heat-sealing layer 30 can be formed into a layer that flows at a relatively low temperature to exhibit adhesiveness. Therefore, when high heat resistance is not required for the gas barrier film, the heat-sealing layer 30 made of an acrylic homopolymer is preferably used.

When a hot melt adhesive is used, various known resins can be used as long as it is solid at room temperature and can form a heat-sealing layer 30 that flows by heating to exhibit adhesiveness, and commercially available products can also be used. It is possible.
Specifically, 0415BA (acrylic homopolymer) and # 7000 series manufactured by Taisei Fine Chemicals Co., Ltd. are exemplified.

The heat-sealing layer 30 is composed of a styrene-acrylic copolymer (styrene-modified acrylic resin), a urethane-acrylic copolymer (urethane-modified acrylic resin), and an acrylic resin for controlling the glass transition temperature, if necessary. It may contain one or more selected from the above.
By adding these components to the heat-sealing layer 30, the Tg of the heat-sealing layer 30 can be improved. Therefore, when the organic thin film transistor is required to have heat resistance depending on the application or the like, the heat-sealing layer 30 to which these components are added is preferably exemplified.
Further, by adding the styrene-acrylic copolymer to the heat-sealing layer 30, the hardness of the heat-sealing layer 30 can be adjusted, so that the balance of hardness with the object to be attached can be adjusted. By adding the urethane-acrylic copolymer to the heat-sealing layer 30, the adhesion with the inorganic layer 16 can be improved.

The amount of these components added is not limited and may be appropriately set according to the components to be added and the target Tg. However, the amount of these components added is preferably such that the main component of the heat-sealing layer 30 is the above-mentioned amorphous resin, acrylic resin, or the like.

The styrene-acrylic copolymer, the urethane-acrylic copolymer, and the acrylic resin for adjusting the glass transition point are not limited, and various resins used for adjusting Tg such as resins can be used. Commercially available products of these components are also available.
As an example, as the styrene-acrylic copolymer, # 7000 series manufactured by Taisei Fine Chemical Co., Ltd. and the like can be exemplified.
Examples of the urethane-acrylic copolymer include the Acryt (registered trademark) 8UA series manufactured by Taisei Fine Chemicals Co., Ltd., such as the Acryt 8UA347H.
Examples of the acrylic resin for adjusting the glass transition point include PMMA (for example, Dianal (registered trademark) manufactured by Mitsubishi Chemical Corporation) and the like.

The thickness of the heat-sealing layer 30 is not limited, and the distance between the inorganic layer 16 and the electronic device 50 at the end after heat-bonding is sufficiently sufficient depending on the material of the heat-sealing layer 30 and the like. The thickness that can be made thin and that provides sufficient adhesiveness and protective performance of the inorganic layer 16 may be appropriately set. The thickness of the heat-sealing layer 30 is preferably 1 to 30 μm, more preferably 2 to 20 μm, and even more preferably 3 to 10 μm.
By setting the thickness of the heat-sealing layer 30 to 1 μm or more, sufficient adhesion is obtained at the time of transfer, and deterioration of the gas barrier performance at the time of peeling the substrate 32 (after transfer) can be prevented, which is preferable. By setting the thickness of the heat-sealing layer 30 to 30 μm or less, a highly transparent gas barrier film 40 capable of sufficiently reducing the distance between the inorganic layer 16 and the electronic device 50 at the end portion after thermal bonding can be obtained. It is preferable in that the gas barrier film 40 can be made thin and light.

<Electronic device>
The electronic device 50 is a known organic EL device such as an organic EL display and an organic EL lighting device.
In the example shown in FIG. 5, the element substrate 52 and a plurality of organic EL elements 54 formed on the element substrate 52 are shown as the constituent elements of the electronic device 50, but the electronic device 50 has another layer. May be good. For example, an electronic device has a configuration in which an insulating film, a transparent electrode layer (TFT (Thin Film Transistor), a thin film transistor), an insulating film, an organic EL element 54, and an insulating film are sequentially laminated on an element substrate 52. You may. Further, it may have a passivation film that protects the organic EL element 54.

(Element board)
As the element substrate 52, various element substrates used as element substrates in conventional organic EL devices such as resin films and glass substrates can be used.

(Organic EL element)
The organic EL element 54 has the same configuration as the organic EL element of the conventional organic EL device. That is, the organic EL element 54 has a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a cathode, and the like.

Here, the height of the organic EL element 54 is about 0.1 μm to 10 μm. The size of the organic EL element 54 in the plane direction is about 0.1 μm × 0.1 μm to 10 μm × 10 μm.

In the above-described embodiment, the organic EL device is exemplified as the electronic device, but the present invention is not limited to this, and various electronic devices such as a solar cell can be used as the electronic device.
Among them, the electronic device produced by the method for producing an electronic device laminate of the present invention has less damage to the inorganic layer 16 and exhibits high durability and excellent gas barrier performance over a long period of time. It is preferably used for an organic EL device having an element.

Although the method for producing the electronic device laminated body of the present invention and the electronic device laminated body have been described in detail above, the present invention is not limited to the above-mentioned aspects, and variously, as long as the gist of the present invention is not deviated. It may be improved or changed.

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the specific examples shown below.

[Example 1]
<Making a gas barrier film>
A TAC (triacetyl cellulose) film (manufactured by FUJIFILM Corporation, thickness 60 μm, width 1000 mm, length 100 m) is used as the substrate 32, and the sealing layer 12 (organic layer, inorganic layer and heat) is placed on the substrate 32 by the following procedure. A fused layer) was formed.

(Formation of organic layer)
Prepare polyarylate (Unitika Ltd. Unifiedr (registered trademark) M-2000H) and cyclohexanone, weigh them so that the weight ratio is 5:95, dissolve them at room temperature, and apply a coating solution with a solid content concentration of 5%. And said. The Tg of the polyarylate used is 275 ° C. (catalog value).
This coating liquid was applied to the substrate by RtoR using a die coater, and passed through a drying zone at 130 ° C. for 3 minutes. Before touching the first film surface touch roll (roll that touches the surface of the substrate 32 on the sealing layer 12 side), a PE (polyethylene) protective film was attached and then wound up. The thickness of the organic layer 14 formed on the substrate 32 was 2 μm.

(Formation of inorganic layer)
A silicon nitride layer was formed as an inorganic layer 16 on the surface of the organic layer 14 by using a general RtoR CVD apparatus in which a substrate is wound around a drum to form a film.
The CVD equipment includes a CCP-CVD film forming apparatus, a drum that serves as a counter electrode for winding and transporting a substrate, a guide roller that peels off a protective film laminated on an organic layer, a recovery roll that winds up the peeled protective film, and a length. It has a loading portion of a roll around which a long protective film is wound, a guide roller for laminating the protective film on the surface of the film-formed inorganic layer, and the like. As the CVD apparatus, an apparatus having two or more film forming units (depositing apparatus) was used.

The substrate 32 on which the organic layer 14 is formed is sent out from the roll loaded in the loading portion, the protective film is peeled off after passing through the last film surface touch roll before film formation, and the inorganic layer is placed on the exposed organic layer 14. 16 was formed. Two electrodes (film forming units) were used for forming the inorganic layer 16, and silane gas, ammonia gas, and hydrogen gas were used as raw material gases. The supply amount of the raw material gas was 150 sccm for silane gas, 300 sccm for ammonia gas and 500 sccm for hydrogen gas for the first film forming unit, and 150 sccm for silane gas, 350 sccm for ammonia gas and 500 sccm for hydrogen gas for the second film forming unit. In the first film forming unit and the second film forming unit, the plasma excitation power was 2.5 kW, and the frequency of the plasma excitation power was 13.56 MHz. Bias power with a frequency of 0.4 MHz and 0.5 kW was supplied to the drum. The temperature of the drum was controlled to 30 ° C. by a cooling means. The film forming pressure was 50 Pa. A PE protective film was attached to the film surface of the inorganic layer 16 immediately after the film formation, and then wound up. The film thickness of the inorganic layer 16 was 20 nm.

(Formation of heat-sealed layer)
Next, the heat-sealing layer 30 was formed on the surface of the inorganic layer 16 by using a general organic film forming apparatus that forms a film by a coating method using RtoR.
First, an acrylic homopolymer (manufactured by Taisei Fine Chemical Co., Ltd., 0415BA) was prepared and diluted with ethyl acetate to prepare a composition having a solid content concentration of 20% by mass. This acrylic homopolymer is amorphous, and Tg flows at 20 ° C. and 100 ° C. to develop adhesiveness.
This composition was applied to the surface of the inorganic layer 16 using a die coater and then passed through a drying zone at 80 ° C. The transit time of the drying zone was set to 3 minutes. As a result, the composition was dried and cured to form a heat-sealing layer 30 on the surface of the inorganic layer 16.
Prior to the application of the composition, the protective film laminated on the surface of the inorganic layer 16 was peeled off. The thickness of the heat-sealed layer formed on the surface of the inorganic layer 16 was 5 μm.

From the above, a long transfer type gas barrier film wound into a roll was produced. From this long transfer type gas barrier film, a gas barrier film 40 was cut out in a size of 100 mm × 100 mm.

<Manufacturing of organic EL device>
A polyimide layer having a thickness of 100 μm and a size of 100 mm × 100 mm was formed on the glass substrate as the element substrate 52, and the organic EL element 54 was formed on the polyimide layer by the following procedure.

(Formation of organic EL element)
The periphery of this element substrate, 2 mm, was masked with ceramic. Further, the masked element substrate was loaded into a general vacuum vapor deposition apparatus, and the electrode made of metallic aluminum having a thickness of 100 nm was formed by vacuum vapor deposition, and a lithium fluoride layer having a thickness of 1 nm was further formed. .. Next, the following organic compound layers were sequentially formed on the device substrate on which the electrodes and the lithium fluoride layer were formed by vacuum vapor deposition.
-(Light emitting layer and electron transporting layer) Tris (8-hydroxyquinolinato) Aluminum: Film thickness 60 nm
(Second hole transport layer) N, N'-diphenyl-N, N'-dinaphthylbenzidine: film thickness 40 nm
・ (1st hole transport layer) Copper phthalocyanine: Film thickness 10 nm
Further, the device substrate on which these layers are formed is loaded into a general sputtering apparatus, and an ITO thin film having a thickness of 0.2 μm is subjected to DC magnetron sputtering using ITO (Indium Tin Oxide indium tin oxide) as a target. A transparent electrode made of the above was formed to form an organic EL element 54 which is a light emitting element using an organic EL material.

The size of the organic EL element 54 was 10 μm × 10 μm, and the height was 5 μm.
The organic EL elements 54 are squarely arranged on the element substrate 52 at a pitch of 50 μm.
From the above, an electronic device (organic EL device) 50 was manufactured.

<Heat crimping process>
As a bonding device for performing the heat bonding step, a bonding device having a flat plate-shaped table 100 and a roller 102 arranged above the table 100 was used. The table 100 and the roller 102 each have a heating means. Further, the roller 102 was made of silicon rubber. Further, the table 100 and the roller 102 are installed in the decompression chamber, and the inside of the decompression chamber can be decompressed by a rotary pump for bonding.

The temperature of the table 100 was adjusted to 25 ° C., and the temperature of the roller 102 was set to 90 ° C. The pressure in the decompression chamber was 0.1 Pa.
The electronic device 50 produced above was placed on the table 100, and the gas barrier film 40 produced above was superposed on the element forming surface of the electronic device 50. At that time, the heat-sealing layer 30 was made to face the element forming surface side.
While pressing the gas barrier film 40 from the substrate 32 side using the roller 102, the roller 102 was translated from the end to heat-bond the gas barrier film 40 and the electronic device 50.
The moving speed of the roller 102 was set to 1 m / min, and the pressure by the roller was adjusted to 0.3 MPa.

The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 50 nm.
The distance from the end of the gas barrier film 40 to the organic EL element 54 was set to 0.5 mm.

<Peeling process>
After the heat bonding step, the substrate 32 was peeled off at the interface with the organic layer 14.
As described above, an electronic device laminate was produced.

[Example 2]
In the heat crimping step, an electronic device laminate was produced in the same manner as in Example 1 except that the temperature of the table 100 was adjusted to 90 ° C. and the temperature of the roller 102 was set to 30 ° C.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 70 nm.

[Example 3]
An electronic device laminate was produced in the same manner as in Example 1 except that the roller temperature was set to 120 ° C.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 25 nm.
[Example 4]
An electronic device laminate was produced in the same manner as in Example 1 except that a styrene acrylic polymer was added so that the glass transition temperature Tg of the heat-sealed layer was 80 ° C.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 80 nm.
[Example 5]
An electronic device laminate was produced in the same manner as in Example 1 except that the pressure by the roller was set to 1 MPa.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 20 nm.
[Example 6]
An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the inorganic layer was 5 nm.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 50 nm.
[Example 7]
An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the inorganic layer was 100 nm.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 50 nm.
[Example 8]
An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the heat-sealing layer before the heat-bonding step was 10 μm.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 70 nm.
[Example 9]
An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the heat-sealing layer before the heat-bonding step was 2 μm.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 30 nm.
[Example 10]
An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the organic layer was 5 μm.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 60 nm.
[Example 11]
An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the organic layer was 0.5 μm.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 40 nm.
[Example 12]
An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the substrate was 80 μm.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 90 nm.
[Example 13]
An electronic device laminate was produced in the same manner as in Example 1 except that the thickness of the substrate was 40 μm.
The distance between the inorganic layer 16 and the electronic device 50 at the end after crimping was measured and found to be 30 nm.

[Comparative Example 1]
In the production of the gas barrier film, an electronic device laminate was produced in the same manner as in Example 1 except that the gas barrier film was not formed and the gas barrier film was bonded to the electronic device using an adhesive as described below.

(Attachment of gas barrier film using adhesive)
The adhesive is a 50% weight solution prepared by dissolving 48% of epoxy resin (JER1001), 48% of epoxy resin (JER152), and 4% of silane coupling agent (KBM502) in MEK (methyl ethyl ketone). It was supposed to be done.
This adhesive is applied onto the inorganic layer of the gas barrier film to a predetermined thickness, the solvent is sufficiently volatilized, then attached to an electronic device, left in an environment of 100 ° C. for 100 hours to cure, and then electron. A device laminate was produced.
The distance between the inorganic layer and the electronic device at the end after bonding was measured and found to be 1000 nm.

[evaluation]
<Brightness>
Immediately after the electronic device laminates produced in each Example and Comparative Example were produced, each electronic device laminate was made to emit light by applying a voltage of 7 V using a SMU2400 type source measure unit manufactured by Keithler, and the overall brightness was increased. Was measured. Then, it was left for 200 hours in an environment of a temperature of 60 ° C. and a humidity of 90%. After leaving it for 200 hours, the electronic device laminate was turned on in the same manner as described above, and the overall brightness was measured again to measure the rate of decrease in brightness.
AAA: The decrease in brightness is 1% or less.
AA: The decrease in brightness was 1% or more and less than 3%.
A: The decrease in brightness was 3% or more and less than 5%.
B: The decrease in brightness was 5% or more and less than 8%.
C: The decrease in brightness was 8% or more and less than 10%.
D: The decrease in brightness was 10% or more and less than 30%.
E: The decrease in brightness is 30% or more, and it can be easily visually recognized that the light emission is low.
Evaluation is acceptable up to C, and D or less is NG.

<Dark spot>
Further, after leaving it for 200 hours, the electronic device laminate was lit and observed from the sealing layer side with a microscope to confirm the presence or absence of dark spots, and evaluated according to the following criteria.
A: No dark spots were observed B: Dark spots were slightly observed C: Dark spots were clearly observed D: Dark spot area ratio was larger

<Flexibility>
After the electronic device laminates of each Example and Comparative Example were outwardly bent at φ8 mm 100,000 times, the brightness was measured in the same manner as before, and the ratio of the decrease in brightness to the brightness immediately after the production of the electronic device laminate was determined. Evaluation was made based on the same criteria as above.
The results are shown in Table 1 below.

From Table 1, the electronic device laminate produced by the production method of the present invention has less decrease in brightness, less generation of dark spots, and an organic EL device even when left in a high temperature and high humidity environment, as compared with the comparative example. It can be seen that the deterioration of the Further, it can be seen that the electronic device laminate produced by the production method of the present invention has higher flexibility than the comparative example.

Further, from the comparison between Example 1 and Example 2, in the thermal pressure bonding step, it is possible to heat the heat-sealed layer more easily by raising the temperature on the substrate side than on the electronic device side, so that the heat-sealed layer can be easily heated and flowed. It can be seen that the pressure can reduce the distance between the inorganic layer and the electronic device.
Further, from the comparison between Example 1 and Example 3, in the heat-bonding step, the higher the temperature on the substrate side, the easier it is to heat the heat-sealed layer and make it flow easily. It can be seen that the distance to the device can be reduced.
Further, from the comparison between Examples 1 and 4, the lower the glass transition temperature Tg of the heat-sealed layer, the easier it is for the heat-sealed layer to flow by heating. It can be seen that the distance between them can be narrowed.
Further, from the comparison between Example 1 and Example 5, it can be seen that when the pressing force in the thermal pressure bonding step is high, the distance between the inorganic layer and the electronic device can be narrowed.
Further, from the comparison of Examples 1 to 5, it can be seen that the narrower the distance between the inorganic layer and the electronic device, the less the decrease in brightness after the high humidity heat test, the less the occurrence of dark spots, and the higher the durability. In addition, it can be seen that there is little decrease in brightness after the bending test and the flexibility is high.

Further, from the comparison of Examples 1, 6 and 7, when the thickness of the inorganic layer is thin, the gas barrier property is low, so that the durability and flexibility are also low, and when the thickness of the inorganic layer is thick, the flexibility is low. Therefore, it can be seen that 10 nm to 30 nm is preferable.

Further, from the comparison of Examples 1, 8 and 9, the thinner the thickness of the heat-sealing layer (thickness before the heat-bonding process), the smaller the distance between the inorganic layer after heat-bonding and the electronic device. I understand.

Further, from the comparison of Examples 1, 10 and 11, it can be seen that the thinner the organic layer, the smaller the distance between the inorganic layer after thermal pressure bonding and the electronic device. It is considered that this is because if the organic layer is thick, heat is less likely to be transferred to the heat-sealing layer during the heat-bonding process, and the fluidity is lowered.

Further, from the comparison of Examples 1, 12 and 13, it can be seen that the thinner the substrate, the smaller the distance between the inorganic layer after thermal pressure bonding and the electronic device. It is considered that this is because if the substrate is thick, heat is less likely to be transferred to the heat-sealing layer during the heat-bonding process, and the fluidity is lowered.

From the comparison of Examples 6 to 13, it can be seen that the narrower the distance between the inorganic layer and the electronic device, the less the decrease in brightness after the high-humidity heat test, the less the occurrence of dark spots, and the higher the durability. In addition, it can be seen that there is little decrease in brightness after the bending test and the flexibility is high.
From the above results, the effect of the present invention is clear.

10 Electronic device laminate 12 Sealing layer 14 Organic layer 16 Inorganic layer 30 Heat fusion layer 32 Substrate 40 Gas barrier film 50 Electronic device 52 Element substrate 54 Organic EL element 100 Table 102 Roller

Claims (11)

A gas barrier film having a heat-sealing layer, an inorganic layer, and an organic layer in this order, and a substrate on the organic layer side of the sealing layer, which is detachably laminated from the sealing layer, is prepared. And the process to do
A heat crimping step of heating and pressurizing the gas barrier film on an element forming surface having irregularities of an electronic device with the heat fusion layer side toward the element forming surface side.
It has a peeling step of peeling the substrate from the sealing layer.
The thickness of the inorganic layer is 100 nm or less, and the thickness is 100 nm or less.
A method for producing an electronic device laminate having a glass transition temperature of the heat-sealed layer of 20 ° C. to 180 ° C. The electron according to claim 1, wherein in the heat crimping step, the heating temperature and the pressurizing pressure are adjusted so that the distance between the inorganic layer and the electronic device at the end portion after the heat crimping is less than 100 nm. A method for manufacturing a device laminate. The method for producing an electronic device laminate according to claim 1 or 2, wherein the electronic device is an organic electroluminescence device. The method for manufacturing an electronic device laminate according to any one of claims 1 to 3, wherein the gas barrier film is heated and pressurized with a roller in the heat bonding step. The method for manufacturing an electronic device laminate according to any one of claims 1 to 4, wherein heating is performed from the substrate side in the heat crimping step. The method for manufacturing an electronic device laminate according to claim 5, wherein heating is performed from the electronic device side in the heat crimping step. The method for manufacturing an electronic device laminate according to claim 6, wherein the heating temperature on the substrate side is higher than the heating temperature on the electronic device side. The method for producing an electronic device laminate according to any one of claims 1 to 7, wherein the substrate is a triacetyl cellulose film. The method for manufacturing an electronic device laminate according to any one of claims 1 to 8, wherein the thickness of the substrate is 0.1 μm to 100 μm. Electronic devices with uneven element forming surfaces and
It has a heat-sealing layer, an inorganic layer, and a transfer layer having an organic layer in this order, which are laminated on the device forming surface.
The thickness of the inorganic layer is 100 nm or less, and the thickness is 100 nm or less.
The glass transition temperature of the heat-sealed layer is 20 ° C. to 180 ° C.
An electronic device laminate in which the distance between the inorganic layer and the electronic device at the end is 100 nm or less. The electronic device laminate according to claim 10, wherein the electronic device is an organic electroluminescence device.

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